Methods of replacing heat transfer fluids

ABSTRACT

Various uses of tetrafluoropropenes, particularly (HFO-1234) in a variety of applications, including refrigeration equipment, are disclosed. These materials are generally useful as refrigerants for heating and cooling, as blowing agents, as aerosol propellants, as solvent composition, and as fire extinguishing and suppressing agents.

RELATED APPLICATIONS

The present application is related to as a continuation-in-part andclaims the priority benefit of U.S. application Ser. No. 11/375,826,filed Mar. 15, 2006, now pending, which is a continuation-in-part ofU.S. application Ser. No. 10/837,525, filed Apr. 29, 2004, now U.S. Pat.No. 7,279,451. The present application is also related to as acontinuation-in-part and claims the priority benefit of U.S. applicationSer. No. 10/694,273, filed Oct. 27, 2003, now U.S. Pat. No. 7,534,366.The present application is also related to and claims the prioritybenefit of U.S. Provisional Application No. 60/693,853, filed Jun. 24,2005. The present application is also related to as acontinuation-in-part and claims the priority benefit of U.S. applicationSer. No. 11/385,259 filed on Mar. 20, 2006, now pending, which is acontinuation of U.S. application Ser. No. 10/695,212, filed Oct. 27,2003, now abandoned. The present application is also related to as acontinuation-in-part and claims the priority benefit of U.S. applicationSer. No. 10/694,272, filed Oct. 27, 2003, now U.S. Pat. No. 7,230,146.

FIELD OF THE INVENTION

This invention relates to compositions, methods and systems havingutility in numerous applications, including particularly heat transfersystems such as refrigeration systems. In preferred aspects, the presentinvention is directed to refrigerant compositions which comprise atleast one multi-fluorinated olefin of the present invention.

BACKGROUND

Fluorocarbon based fluids have found widespread use in many commercialand industrial applications, including as the working fluid in systemssuch as air conditioning, heat pump and refrigeration systems, asaerosol propellants, as blowing agents, as heat transfer media, and asgaseous dielectrics. Because of certain suspected environmentalproblems, including the relatively high global warming potentials,associated with the use of some of the compositions that have heretoforebeen used in these applications, it has become increasingly desirable touse fluids having low or even zero ozone depletion potential, such ashydrofluorocarbons (“HFCs”). Thus, the use of fluids that do not containchlorofluorocarbons (“CFCs”) or hydrochlorofluorocarbons (“HCFCs”) isdesirable. Furthermore, some HFC fluids may have relatively high globalwarming potentials associated therewith, and it is desirable to usehydrofluorocarbon or other fluorinated fluids having as low globalwarming potentials as possible while maintaining the desired performancein use properties. Additionally, the use of single component fluids orazeotrope-like mixtures, which do not substantially fractionate onboiling and evaporation, is desirable in certain circumstances.

Certain fluorocarbons have been a preferred component in many heatexchange fluids, such as refrigerants, for many years in manyapplications. For, example, fluoroalkanes, such as chlorofluoromethaneand chlorofluoroethane derivatives, have gained widespread use asrefrigerants in applications including air conditioning and heat pumpapplications owing to their unique combination of chemical and physicalproperties. Many of the refrigerants commonly utilized in vaporcompression systems are either single components fluids or azeotropicmixtures.

As suggested above, concern has been increasing in recent years aboutpotential damage to the earth's atmosphere and climate, and certainchlorine-based compounds have been identified as particularlyproblematic in this regard. The use of chlorine-containing compositions(such as chlorofluorocarbons (CFC's), hydrochlorofluorocarbons (HCF's)and the like) as the working fluid in heat transfer systems, such as inrefrigeration and air-conditioning systems, has become disfavoredbecause of the ozone-depleting properties associated with many of suchcompounds. There has thus been an increasing need for new fluorocarbonand hydrofluorocarbon compounds and compositions that are attractivealternatives to the compositions heretofore used in these and otherapplications. For example, it has become desirable to retrofitchlorine-containing refrigeration systems by replacingchlorine-containing refrigerants with non-chlorine-containingrefrigerant compounds that will not deplete the ozone layer, such ashydrofluorocarbons (HFC's). Industry in general and the heat transferindustry in particular are continually seeking new fluorocarbon basedmixtures that offer alternatives to, and are considered environmentallysafer substitutes for, CFCs and HCFCs. It is generally consideredimportant, however, at least with respect to heat transfer fluids, thatany potential substitute must also possess those properties present inmany of the most widely used fluids, such as excellent heat transferproperties, chemical stability, low- or no-toxicity, non-flammabilityand/or lubricant compatibility, among others.

Applicants have come to appreciate that lubricant compatibility is ofparticular importance in many of applications. More particularly, it ishighly desirably for refrigeration fluids to be compatible with thelubricant utilized in the compressor unit, used in most refrigerationsystems. Unfortunately, many non-chlorine-containing refrigerationfluids, including HFC's, are relatively insoluble and/or immiscible inthe types of lubricants used traditionally with CFC's and HFC's,including, for example, mineral oils, alkylbenzenes orpoly(alpha-olefins). In order for a refrigeration fluid-lubricantcombination to work at a desirable level of efficiently within acompression refrigeration, air-conditioning and/or heat pump system, thelubricant should be sufficiently soluble in the refrigeration liquidover a wide range of operating temperatures. Such solubility lowers theviscosity of the lubricant and allows it to flow more easily throughoutthe system. In the absence of such solubility, lubricants tend to becomelodged in the coils of the evaporator of the refrigeration,air-conditioning or heat pump system, as well as other parts of thesystem, and thus reduce the system efficiency.

With regard to efficiency in use, it is important to note that a loss inrefrigerant thermodynamic performance or energy efficiency may havesecondary environmental impacts through increased fossil fuel usagearising from an increased demand for electrical energy.

Furthermore, it is generally considered desirably for CFC refrigerantsubstitutes to be effective without major engineering changes toconventional vapor compression technology currently used with CFCrefrigerants.

Flammability is another important property for many applications. Thatis, it is considered either important or essential in many applications,including particularly in heat transfer applications, to usecompositions which are non-flammable. Thus, it is frequently beneficialto use in such compositions compounds which are nonflammable. As usedherein, the term “nonflammable” refers to compounds or compositionswhich are determined to be nonflammable as determined in accordance withASTM standard E-681, dated 2002, which is incorporated herein byreference. Unfortunately, many HFC's which might otherwise be desirablefor used in refrigerant compositions are not nonflammable. For example,the fluoroalkane difluoroethane (HFC-152a) and the fluoroalkene1,1,1-trifluorpropene (HFO-1243zf) are each flammable and therefore notviable for use in many applications.

Higher fluoroalkenes, that is fluorine-substituted alkenes having atleast five carbon atoms, have been suggested for use as refrigerants.U.S. Pat. No. 4,788,352—Smutny is directed to production of fluorinatedC₅ to C₈ compounds having at least some degree of unsaturation. TheSmutny patent identifies such higher olefins as being known to haveutility as refrigerants, pesticides, dielectric fluids, heat transferfluids, solvents, and intermediates in various chemical reactions. (Seecolumn 1, lines 11-22).

While the fluorinated olefins described in Smutny may have some level ofeffectiveness in heat transfer applications, it is believed that suchcompounds may also have certain disadvantages. For example, some ofthese compounds may tend to attack substrates, particularlygeneral-purpose plastics such as acrylic resins and ABS resins.Furthermore, the higher olefinic compounds described in Smutny may alsobe undesirable in certain applications because of the potential level oftoxicity of such compounds which may arise as a result of pesticideactivity noted in Smutny. Also, such compounds may have a boiling pointwhich is too high to make them useful as a refrigerant in certainapplications.

Bromofluoromethane and bromochlorofluoromethane derivatives,particularly bromotrifluoromethane (Halon 1301) andbromochlorodifluoromethane (Halon 1211) have gained widespread use asfire extinguishing agents in enclosed areas such as airplane cabins andcomputer rooms. However, the use of various halons is being phased outdue to their high ozone depletion. Moreover, as halons are frequentlyused in areas where humans are present, suitable replacements must alsobe safe to humans at concentrations necessary to suppress or extinguishfire.

Applicants have thus come to appreciate a need for compositions, andparticularly heat transfer compositions, fire extinguishing/suppressioncompositions, blowing agents, solvent compositions, and compatabilizingagents, that are potentially useful in numerous applications, includingvapor compression heating and cooling systems and methods, whileavoiding one or more of the disadvantages noted above.

SUMMARY

Applicants have found that the above-noted need, and other needs, can besatisfied by compositions, preferably heat transfer compositions,comprising one or more C3 to C6 fluorakenes, and more preferably one ormore C3, C4, or C5 fluoroalkenes, preferably compounds having Formula Ias follows:XCF_(z)R_(3-z)  (I)where X is a C₂, C₃, C₄ or C₅ unsaturated, substituted or unsubstituted,radical, each R is independently Cl, F, Br, I or H, and z is 1 to 3. Incertain preferred embodiments, the fluoroalkene of the present inventionhas at least four (4) halogen substituents, at least three of which areF and even more preferably none of which are Br. In certain preferredembodiments, the compound of formula one comprises a compound, andpreferably a three carbon compound, in which each non-terminalunsaturated carbon has a fluorine substituent.

For embodiments in which at least one Br substituent is present, it ispreferred that the compound includes no hydrogen. In such embodiments italso generally preferred that the Br substituent is on an unsaturatedcarbon, and even more preferably the Br substituent is on annon-terminal unsaturated carbon. One particularly preferred embodimentin this class is CF₃CBr═CF₂, including all of its isomers.

In certain embodiments it is highly preferred that the compounds ofFormula I comprise propenes, butenes, pentanes and hexanes having from 3to 5 fluorine substituents, with other substituents being either presentor not present. In certain preferred embodiments, no R is Br, andpreferably the unsaturated radical contains no Br substituents. Amongthe propenes, tetrafluoropropenes (HFO-1234) and fluorochloropropenes(such as trifluoro, monochloropropenes (HFCO-1233), and even morepreferably CF₃CCl═CH₂ (HFO-1233xf) and CF₃CH═CHCl (HFO-1233zd)) areespecially preferred in certain embodiments.

In certain embodiments, pentafluoropropenes are preferred, includingparticularly those pentafluoropropenes in which there is a hydrogensubstituent on the terminal unsaturated carbon, such as CF₃CF═CFH(HFO-1225yez and/or yz), particularly since applicants have discoveredthat such compounds have a relatively low degree of toxicity incomparison to at least the compound CF₃CH═CF₂(HFO-1225zc).

Among the butenes, fluorochlorobutenes are especially preferred incertain embodiments.

The term “HFO-1234” is used herein to refer to all tetrafluoropropenes.Among the tetrafluoropropenes are included 1,1,1,2-tetrafluoropropene(HFO-1234yf) and both cis- and trans-1,1,1,3-tetrafluoropropene(HFO-1234ze). The term HFO-1234ze is used herein generically to refer to1,1,1,3-tetrafluoropropene, independent of whether it is the cis- ortrans-form. The terms “cisHFO-1234ze” and “transHFO-1234ze” are usedherein to describe the cis- and trans-forms of1,1,1,3-tetrafluoropropene respectively. The term “HFO-1234ze” thereforeincludes within its scope cisHFO-1234ze, transHFO-1234ze, and allcombinations and mixtures of these.

The term “HFO-1233” is used herein to refer to all trifluoro,monochloropropenes. Among the trifluoro, monochloropropenes are included1,1,1,trifluoro-2, chloro-propene (HFCO-1233xf), both cis- andtrans-1,1,1-trifluo-3, chlororopropene (HFCO-1233zd). The termHFCO-1233zd is used herein generically to refer to 1,1,1-trifluo-3,chloro-propene, independent of whether it is the cis- or trans-form. Theterms “cisHFCO-1233zd” and “transHFCO-1233zd” are used herein todescribe the cis- and trans-forms of 1,1,1-trifluo, 3-chlororopropene,respectively. The term “HFCO-1233zd” therefore includes within its scopecisHFCO-1233zd, transHFCO-1233zd, and all combinations and mixtures ofthese.

The term “HFO-1225” is used herein to refer to all pentafluoropropenes.Among such molecules are included 1,1,1,2,3 pentafluoropropene(HFO-1225yez), both cis- and trans-forms thereof. The term HFO-1225yezis thus used herein generically to refer to 1,1,1,2,3pentafluoropropene, independent of whether it is the cis- or trans-form.The term “HFO-1225yez” therefore includes within its scopecisHFO-1225yez, transHFO-1225yez, and all combinations and mixtures ofthese.

In certain preferred embodiments, the present compositions comprise acombination of two or more compounds of Formula I. In one such preferredembodiment the composition comprises at least one tetrafluoropropene andat least one pentafluoropropene compound, preferably with each compoundbeing present in the composition in an amount of from about 20% byweight to about 80% by weight, more preferably from about 30% by weightto about 70% by weight, and even more preferably from about 40% byweight to about 60% by weight. In certain of such embodiments, thetetrafluoropropene comprises, and preferably consists essentially ofHFO-1234 (most preferably HFO-1234yf) and HFO1225 (most preferablyHFO-1225yez).

The present invention provides also methods and systems which utilizethe compositions of the present invention, including methods and systemsfor heat transfer, for retrofitting existing heat transfer equipment,for replacing the existing heat transfer fluids in an existing heattransfer system. In certain cases, the present compositions may also beused in connection with foam blowing, solvating, flavor and fragranceextraction and/or delivery, aerosol generation, non-aerosol propellantsand as inflating agents.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 provides a sketch of the vessel as discussed in Example 5.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The Compositions

The preferred embodiments of the present invention are directed tocompositions comprising at least one fluoroalkene containing from 3 to 6carbon atoms, preferably 3 to five carbon atoms, and in certain highlypreferred embodiments three carbon atoms, and at least one carbon-carbondouble bond. The fluoroalkene compounds of the present invention aresometimes referred to herein for the purpose of convenience ashydrofluoro-olefins or “HFOs” if they contain at least one hydrogen.Although it is contemplated that the HFOs of the present invention maycontain two carbon-carbon double bonds, such compounds at the presenttime are not considered to be preferred. For HFOs which also contain atleast one chlorine atom, the designation HFCO is sometimes used herein

As mentioned above, the present compositions comprise one or morecompounds in accordance with Formula I. In preferred embodiments, thecompositions include compounds of Formula II below:

where each R is independently Cl, F, Br, I or H,

R′ is (CR₂)_(n)Y,

Y is CRF₂

and n is 0, 1, 2 or 3, preferably 0 or 1, it being generally preferredhowever that when Br is present in the compound there is no hydrogen inthe compound. In certain embodiments, Br is not present in the compound.

In highly preferred embodiments, Y is CF₃, n is 0 or 1 (most preferably0) and at least one of the remaining Rs is F, and preferably no R is Bror when Br is present, there is no hydrogen in the compound.

Applicants believe that, in general, the compounds of the aboveidentified Formulas I and II are generally effective and exhibit utilityin heat transfer compositions generally and in refrigerant compositionsparticularly. The compositions of the present invention also find use asblowing agent compositions, compatibilizers, aerosols, propellants,fragrances, flavor formulations, solvent compositions and inflatingagent composition. However, applicants have surprisingly andunexpectedly found that certain of the compounds having a structure inaccordance with the formulas described above exhibit a highly desirablelow level of toxicity compared to other of such compounds. As can bereadily appreciated, this discovery is of potentially enormous advantageand benefit for the formulation of not only refrigerant compositions,but also any and all compositions which would otherwise containrelatively toxic compounds satisfying the formulas described above. Moreparticularly, applicants believe that a relatively low toxicity level isassociated with compounds of Formula II, preferably wherein Y is CF₃, nis 0 or 1, wherein at least one R on the unsaturated terminal carbon isH, and at least one of the remaining Rs is F or Cl. Applicants believealso that all structural, geometric and stereoisomers of such compoundsare effective and of beneficially low toxicity.

In certain preferred embodiments the compounds of the present inventioncomprise one or more comprises a C3 or C4 HFO, preferably a C3 HFO, andpreferably a compound accordance with Formula I in which X is a halogensubstituted C₃ alkylene and z is 3. In certain of such embodiments X isfluorine and/or chlorine substituted C₃ alkylene, with the following C₃alkylene radicals being preferred in certain embodiments:

—CH═CF—CH₃

—CF═CH—CH₃

—CH₂—CF═CH₂

—CH₂—CH═CFH,

Such embodiments therefore comprise the following preferred compounds:CF₃—CH═CF—CH₃; CF₃—CF═CH—CH₃; CF₃—CH₂—CF═CH₂; CF₃—CH₂—CH═CFH; andcombinations of these with one another and/or with other compounds inaccordance with Formula I,

In certain preferred embodiments, the compound of the present inventioncomprises a C3 or C4 HFCO, preferably a C3 HFCO, and more preferably acompound in accordance with Formula II in which Y is CF₃, n is 0, atleast one R on the unsaturated terminal carbon is H, and at least one ofthe remaining Rs is Cl. HFCO-1233 is an example of such a preferredcompound.

In highly preferred embodiments, especially embodiments which comprisethe low toxicity compounds described above, n is zero. In certain highlypreferred embodiments the compositions of the present invention compriseone or more tetrafluoropropenes, including HFO-1234yf, (cis)HFO-1234zeand (trans)HFO-1234ze, with HFO-1234ze being generally preferred.Although the properties of (cis)HFO-1234ze and (trans)HFO-1234ze differin at least some respects, it is contemplated that each of thesecompounds is adaptable for use, either alone or together with othercompounds including its stereo isomer, in connection with each of theapplications, methods and systems described herein. For example,(trans)HFO-1234ze may be preferred for use in certain systems because ofits relatively low boiling point (−19° C.), while (cis)HFO-1234ze, witha boiling point of +9° C., may be preferred in other applications. Ofcourse, it is likely that combinations of the cis- and trans-isomerswill be acceptable and/or preferred in many embodiments. Accordingly, itis to be understood that the terms “HFO-1234ze” and1,3,3,3-tetrafluoropropene refer to both stereo isomers, and the use ofthis term is intended to indicate that each of the cis- and trans-formsapplies and/or is useful for the stated purpose unless otherwiseindicated.

HFO-1234 compounds are known materials and are listed in ChemicalAbstracts databases. The production of fluoropropenes such as CF₃CH═CH₂by catalytic vapor phase fluorination of various saturated andunsaturated halogen-containing C₃ compounds is described in U.S. Pat.Nos. 2,889,379; 4,798,818 and 4,465,786, each of which is incorporatedherein by reference. EP 974,571, also incorporated herein by reference,discloses the preparation of 1,1,1,3-tetrafluoropropene by contacting1,1,1,3,3-pentafluoropropane (HFC-245fa) in the vapor phase with achromium-based catalyst at elevated temperature, or in the liquid phasewith an alcoholic solution of KOH, NaOH, Ca(OH)₂ or Mg(OH)₂. Inaddition, methods for producing compounds in accordance with the presentinvention are described generally in connection with U.S. Pat. No.7,230,146, which is also incorporated herein by reference.

Other preferred compounds for use in accordance with the presentinvention include pentafluoropropenes, including all isomers thereof(eg., HFO-1225), tetra- and penta-fluorobutenes, including all isomersthereof (eg., HFO-1354 and HFO-1345). Of course, the presentcompositions may comprise combinations of any two or more compoundswithin the broad scope of the invention or within any preferred scope ofthe invention.

The present compositions, particularly those comprising HFO-1234(including HFO-1234ze and HFO-1234yf), are believed to possessproperties that are advantageous for a number of important reasons. Forexample, applicants believe, based at least in part on mathematicalmodeling, that the fluoroolefins of the present invention will not havea substantial negative affect on atmospheric chemistry, being negligiblecontributors to ozone depletion in comparison to some other halogenatedspecies. The preferred compositions of the present invention thus havethe advantage of not contributing substantially to ozone depletion. Thepreferred compositions also do not contribute substantially to globalwarming compared to many of the hydrofluoroalkanes presently in use.

Of course other compounds and/or components that modulate a particularproperty of the compositions (such as cost for example) may also beincluded in the present compositions, and the presence of all suchcompounds and components is within the broad scope of the invention.

In certain preferred forms, compositions of the present invention have aGlobal Warming Potential (GWP) of not greater than about 1000, morepreferably not greater than about 500, and even more preferably notgreater than about 150. In certain embodiments, the GWP of the presentcompositions is not greater than about 100 and even more preferably notgreater than about 75. As used herein, “GWP” is measured relative tothat of carbon dioxide and over a 100 year time horizon, as defined in“The Scientific Assessment of Ozone Depletion, 2002, a report of theWorld Meteorological Association's Global Ozone Research and MonitoringProject,” which is incorporated herein by reference.

In certain preferred forms, the present compositions also preferablyhave an Ozone Depletion Potential (ODP) of not greater than 0.05, morepreferably not greater than 0.02 and even more preferably about zero. Asused herein, “ODP” is as defined in “The Scientific Assessment of OzoneDepletion, 2002, A report of the World Meteorological Association'sGlobal Ozone Research and Monitoring Project,” which is incorporatedherein by reference.

The amount of the Formula I compounds, particularly HFO-1234, and evenmore preferably HFO-1234yf, contained in the present compositions canvary widely, depending the particular application, and compositionscontaining more than trace amounts and less than 100% of the compoundare within broad the scope of the present invention. Moreover, thecompositions of the present invention can be azeotropic, azeotrope-likeor non-azeotropic. In preferred embodiments, the present compositionscomprise Formula I compounds, preferably HFO-1234 and more preferablyHFO-1234ze and/or HFO-1234yf, preferably HFO-1234ze and/or HFO-1234yf,in amounts from about 5% by weight to about 99% by weight, and even morepreferably from about 5% to about 95%. Many additional compounds orcomponents, including lubricants, stabilizers, metal passivators,corrosion inhibitors, flammability suppressants, and other compoundsand/or components that modulate a particular property of thecompositions (such as cost for example) may be included in the presentcompositions, and the presence of all such compounds and components iswithin the broad scope of the invention. In certain preferredembodiments, the present compositions include, in addition to thecompounds of formula I (including particularly HFO-1234ze and/orHFO-1234yf), one or more of the following:

Trichlorofluoromethane (CFC-11)

Dichlorodifluoromethane (CFC-12)

Difluoromethane (HFC-32)

Pentafluoroethane (HFC-125)

1,1,2,2-tetrafluoroethane (HFC-134)

1,1,1,2-Tetrafluoroethane (HFC-134a)

Difluoroethane (HFC-152a)

1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea)

1,1,1,3,3,3-hexafluoropropane (HFC-236fa)

1,1,1,3,3-pentafluoropropane (HFC-245fa)

1,1,1,3,3-pentafluorobutane (HFC-365mfc)

water

CO₂

The relative amount of any of the above noted compounds of the presentinvention, as well as any additional components which may be included inpresent compositions, can vary widely within the general broad scope ofthe present invention according to the particular application for thecomposition, and all such relative amounts are considered to be withinthe scope hereof.

Accordingly, applicants have recognized that certain compositions of thepresent invention can be used to great advantage in a number ofapplications. For example, included in the present invention are methodsand compositions relating to heat transfer applications, foam andblowing agent applications, propellant applications, sprayablecomposition applications, sterilization applications, aerosolapplications, compatibilizer application, fragrance and flavorapplications, solvent applications, cleaning applications, inflatingagent applications and others. It is believed that those of skill in theart will be readily able to adapt the present compositions for use inany and all such applications without undue experimentation.

The present compositions are generally useful as replacements for CFCs,such as dichlorodifluoromethane (CFC-12), HCFCs, such aschlorodifluoromethane (HCFC-22), HFCs, such as tetrafluoroethane(HFC-134a), and combinations of HFCs and CFCs, such as the combinationof CFC-12 and 1,1-difluoroethane (HFC-152a) (the combinationCFC-12:HFC-152a in a 73.8:26.2 mass ratio being known as R-500) inrefrigerant, aerosol, and other applications.

Heat Transfer Compositions

The compositions of the present invention are generally adaptable foruse in heat transfer applications, that is, as a heating and/or coolingmedium, including as evaporative cooling agents.

In connection with evaporative cooling applications, the compositions ofthe present invention are brought in contact, either directly orindirectly, with a body to be cooled and thereafter permitted toevaporate or boil while in such contact, with the preferred result thatthe boiling gas in accordance with the present composition absorbs heatfrom the body to be cooled. In such applications it may be preferred toutilize the compositions of the present invention, preferably in liquidform, by spraying or otherwise applying the liquid to the body to becooled. In other evaporative cooling applications, it may be preferredto permit a liquid composition in accordance with the present intentionto escape from a relatively high pressure container into a relativelylower pressure environment wherein the body to be cooled is in contact,either directly or indirectly, with the container enclosing the liquidcomposition of the present invention, preferably without recovering orrecompressing the escaped gas. One particular application for this typeof embodiment is the self cooling of a beverage, food item, novelty itemor the like. Previous to the invention described herein, priorcompositions, such as HFC-152a and HFC-134a were used for suchapplications. However, such compositions have recently been looked uponnegatively in such application because of the negative environmentalimpact caused by release of these materials into the atmosphere. Forexample, the United States EPA has determined that the use of such priorchemicals in this application is unacceptable due to the high globalwarming nature of these chemicals and the resulting detrimental effecton the environment that may result from their use. The compositions ofthe present invention should have a distinct advantage in this regarddue to their low global warming potential and low ozone depletionpotential, as described herein. Additionally, the present compositionsare expected to also find substantial utility in connection with thecooling of electrical or electronic components, either duringmanufacture or during accelerated lifetime testing. In a acceleratedlifetime testing, the component is sequentially heated and cooled inrapid succession to simulate the use of the component. Such uses wouldtherefore be of particular advantage in the semiconductor and computerboard manufacturing industry. Another advantage of the presentcompositions in this regard is they are expected to exhibit ascontagious electrical properties when used in connection with suchapplications. Another evaporative cooling application comprises methodsfor temporarily causing a discontinuation of the flow of fluid through aconduit. Preferably, such methods would include contacting the conduit,such as a water pipe through which water is flowing, with a liquidcomposition according to the present invention and allowing the liquidcomposition of the present invention to evaporate while in contact withthe conduit so as to freeze liquid contained therein and therebytemporarily stop the flow of fluid through the conduit. Such methodshave distinct advantage in connection with enabling the service or otherwork to be performed on such conduits, or systems connected to suchconduits, at a location downstream of the location at which the presentcomposition is applied.

Although it is contemplated that the compositions of the presentinvention may include the compounds of the present invention in widelyranging amounts, it is generally preferred that refrigerant compositionsof the present invention comprise compound(s) in accordance with FormulaI, more preferably in accordance with Formula II, and even morepreferably HFO-1234 (including HFO-1234ze and HFO-1234yf), in an amountthat is at least about 50% by weight, and even more preferably at leastabout 70% by weight, of the composition. In certain embodiments, it ispreferred that the heat transfer compositions of the present inventioncomprise transHFO-1234ze. In certain preferred embodiments, it ispreferred that the heat transfer compositions of the present inventioncomprise at least about 80%, and even more preferably at least about 90%by weight of HFO-1234, and even more preferably HFO-1234yf and/orHFO-1234ze. The heat transfer compositions of the present inventioncomprise in certain embodiments a combination of cisHFO-1234ze andtransHFO1234ze, preferably in a cis:trans weight ratio of from about1:99 to about 10:99, more preferably from about 1:99 to about 5:95, andeven more preferably from about 1:99 to about 3:97.

The relative amount of the hydrofluoroolefin used in accordance with thepresent invention is preferably selected to produce a heat transferfluid which has the required heat transfer capacity, particularlyrefrigeration capacity, and preferably is at the same timenon-flammable. As used herein, the term non-flammable refers to a fluidwhich is non-flammable in all proportions in air as measured by ASTME-681.

The compositions of the present invention may include other componentsfor the purpose of enhancing or providing certain functionality to thecomposition, or in some cases to reduce the cost of the composition. Forexample, refrigerant compositions according to the present invention,especially those used in vapor compression systems, include a lubricant,generally in amounts of from about 30 to about 50 percent by weight ofthe composition. Furthermore, the present compositions may also includea co-refrigerant, or compatibilizer, such as propane, for the purpose ofaiding compatibility and/or solubility of the lubricant. Suchcompatibilizers, including propane, butanes and pentanes, are preferablypresent in amounts of from about 0.5 to about 5 percent by weight of thecomposition. Combinations of surfactants and solubilizing agents mayalso be added to the present compositions to aid oil solubility, asdisclosed by U.S. Pat. No. 6,516,837, the disclosure of which isincorporated by reference. Commonly used refrigeration lubricants suchas Polyol Esters (POEs) and Poly Alkylene Glycols (PAGs), PAG oils,silicone oil, mineral oil, alkyl benzenes (ABs) and poly(alpha-olefin)(PAO) that are used in refrigeration machinery with hydrofluorocarbon(HFC) refrigerants may be used with the refrigerant compositions of thepresent invention. Commercially available mineral oils include Witco LP250 (registered trademark) from Witco, Zerol 300 (registered trademark)from Shrieve Chemical, Sunisco 3GS from Witco, and Calumet R015 fromCalumet. Commercially available alkyl benzene lubricants include Zerol150 (registered trademark). Commercially available esters includeneopentyl glycol dipelargonate, which is available as Emery 2917(registered trademark) and Hatcol 2370 (registered trademark). Otheruseful esters include phosphate esters, dibasic acid esters, andfluoroesters. In some cases, hydrocarbon based oils are have sufficientsolubility with the refrigerant that is comprised of an iodocarbon, thecombination of the iodocarbon and the hydrocarbon oil might more stablethan other types of lubricant. Such combination may therefore beadvantageous. Preferred lubricants include polyalkylene glycols andesters. Polyalkylene glycols are highly preferred in certain embodimentsbecause they are currently in use in particular applications such asmobile air-conditioning. Of course, different mixtures of differenttypes of lubricants may be used.

In certain preferred embodiments, the heat transfer compositioncomprises from about 10% to about 95% by weight of a compound of FormulaI, more preferably a compound of Formula II, and even more preferablyone or more HFO-1234 compounds, and from about 5% to about 90% by weightof an adjuvant, particular in certain embodiments a co-refrigerant (suchas HFC-152, HFC-125 and/or CF₃I). The use of the term co-refrigerant isnot intended for use herein in a limiting sense regarding the relativeperformance of the compound of Formula I compounds, but is used in steadused to identify other components of the refrigerant compositiongenerally that contribute to the desirable heat transfer characteristicsof the composition for a desired application. In certain of suchembodiments the co-refrigerant comprises, and preferably consistsessentially of, one or more HFCs and/or one or more fluoroiodo C1-C3compounds, such as trifluroiodomethane, and combinations of these witheach other and with other components.

In preferred embodiments in which the co-refrigerant comprises HFC,preferably HFC-125. the composition comprises HFC in an amount of fromabout 50% by weight to about 95% by weight of the total heat transfercomposition, more preferably from about 60% by weight to about 90% byweight, and even more preferably of from about 70% to about 90% byweight of the composition. In such embodiments the compound of thepresent invention preferably comprises, and even more preferablyconsists essentially of, HFO-1234, and even more preferably HFO-1234yfand/or HFO-1234ze in an amount of from about 5% by weight to about 50%by weight of the total heat transfer composition, more preferably fromabout 10% by weight to about 40% by weight, and even more preferably offrom about 10% to about 30% by weight of the composition.

In preferred embodiments in which the co-refrigerant comprisesfluoriodocarbon, preferably CF3I, the composition comprisesfluoriodocarbon in an amount of from about 15% by weight to about 50% byweight of the total heat transfer composition, more preferably fromabout 20% by weight to about 40% by weight, and even more preferably offrom about 25% to about 35% by weight of the composition. In suchembodiments the compound of the present invention preferably comprises,and even more preferably consists essentially of, HFO-1234, and evenmore preferably HFO-1234yf in an amount of from about 50% by weight toabout 90% by weight of the total heat transfer composition, morepreferably from about 60% by weight to about 80% by weight, and evenmore preferably of from about 65% to about 75% by weight of thecomposition.

The present methods, systems and compositions are thus adaptable for usein connection with a wide variety of heat transfer systems in generaland refrigeration systems in particular, such as air-conditioning(including both stationary and mobile air conditioning systems),refrigeration, heat-pump systems, and the like. In certain preferredembodiments, the compositions of the present invention are used inrefrigeration systems originally designed for use with an HFCrefrigerant, such as, for example, HFC-134a, or an HCFC refrigerant,such as, for example, HCFC-22. The preferred compositions of the presentinvention tend to exhibit many of the desirable characteristics ofHFC-134a and other HFC refrigerants, including a GWP that is as low, orlower than that of conventional HFC refrigerants and a capacity that isas high or higher than such refrigerants and a capacity that issubstantially similar to or substantially matches, and preferably is ashigh as or higher than such refrigerants. In particular, applicants haverecognized that certain preferred embodiments of the presentcompositions tend to exhibit relatively low global warming potentials(“GWPs”), preferably less than about 1000, more preferably less thanabout 500, and even more preferably less than about 150. In addition,the relatively constant boiling nature of certain of the presentcompositions, including the azeotrope-like compositions described in theco-pending patent applications incorporated herein by reference, makesthem even more desirable than certain conventional HFCs, such as R-404Aor combinations of HFC-32, HFC-125 and HFC-134a (the combinationHFC-32:HFC-125:HFC134a in approximate 23:25:52 weight ratio is referredto as R-407C), for use as refrigerants in many applications. Heattransfer compositions of the present invention are particularlypreferred as replacements for HFC-134, HFC-152a, HFC-22, R-12 and R-500.

In certain other preferred embodiments, the present compositions areused in refrigeration systems originally designed for use with aCFC-refrigerant. Preferred refrigeration compositions of the presentinvention may be used in refrigeration systems containing a lubricantused conventionally with CFC-refrigerants, such as mineral oils,polyalkylbenzene, polyalkylene glycol oils, and the like, or may be usedwith other lubricants traditionally used with HFC refrigerants. As usedherein the term “refrigeration system” refers generally to any system orapparatus, or any part or portion of such a system or apparatus, whichemploys a refrigerant to provide cooling. Such refrigeration systemsinclude, for example, air conditioners, electric refrigerators, chillers(including chillers using centrifugal compressors), transportrefrigeration systems, commercial refrigeration systems and the like.

Many existing refrigeration systems are currently adapted for use inconnection with existing refrigerants, and the compositions of thepresent invention are believed to be adaptable for use in many of suchsystems, either with or without system modification. Many applicationsthe compositions of the present invention may provide an advantage as areplacement in smaller systems currently based on certain refrigerants,for example those requiring a small refrigerating capacity and therebydictating a need for relatively small compressor displacements.Furthermore, in embodiments where it is desired to use a lower capacityrefrigerant composition of the present invention, for reasons ofefficiency for example, to replace a refrigerant of higher capacity,such embodiments of the present compositions provide a potentialadvantage. Thus, it is preferred in certain embodiments to usecompositions of the present invention, particularly compositionscomprising a substantial proportion of, and in some embodimentsconsisting essentially of the present compositions, as a replacement forexisting refrigerants, such as: HFC-134a; CFC-12; HCFC-22; HFC-152a;combinations of pentfluoroethane (HFC-125), trifluorethane (HFC-143a)and tetrafluoroethane (HFC-134a) (the combinationHFC-125:HFC-143a:HFC134a in approximate 44:52:4 weight ratio is referredto as R-404A); combinations of HFC-32, HFC-125 and HFC-134a (thecombination HFC-32:HFC-125:HFC134a in approximate 23:25:52 weight ratiois referred to as R-407C); combinations of methylene fluoride (HFC-32)and pentfluoroethane (HFC-125) (the combination HFC-32:HFC-125 inapproximate 50:50 weight ratio is referred to as R-410A); thecombination of CFC-12 and 1,1-difluorethane (HFC-152a) (the combinationCFC-12:HFC-152a in a 73.8:26.2 weight ratio is referred to R-500); andcombinations of HFC-125 and HFC-143a (the combination HFC-125:HFC143a inapproximate 50:50 weight ratio is referred to as R-507A). In certainembodiments it may also be beneficial to use the present compositions inconnection with the replacement of refrigerants formed from thecombination HFC-32:HFC-125:HFC134a in approximate 20:40:40 weight ratio,which is referred to as R-407A, or in approximate 15:15:70 weight ratio,which is referred to as R-407D. The present compositions are alsobelieved to be suitable as replacements for the above noted compositionsin other applications, such as aerosols, blowing agents and the like, asexplained elsewhere herein.

In certain applications, the refrigerants of the present inventionpotentially permit the beneficial use of larger displacementcompressors, thereby resulting in better energy efficiency than otherrefrigerants, such as HFC-134a. Therefore the refrigerant compositionsof the present invention provide the possibility of achieving acompetitive advantage on an energy basis for refrigerant replacementapplications, including automotive air conditioning systems and devices,commercial refrigeration systems and devices, chillers, residentialrefrigerator and freezers, general air conditioning systems, heat pumpsand the like.

Many existing refrigeration systems are currently adapted for use inconnection with existing refrigerants, and the compositions of thepresent invention are believed to be adaptable for use in many of suchsystems, either with or without system modification. In manyapplications the compositions of the present invention may provide anadvantage as a replacement in systems which are currently based onrefrigerants having a relatively high capacity. Furthermore, inembodiments where it is desired to use a lower capacity refrigerantcomposition of the present invention, for reasons of cost for example,to replace a refrigerant of higher capacity, such embodiments of thepresent compositions provide a potential advantage. Thus, It ispreferred in certain embodiments to use compositions of the presentinvention, particularly compositions comprising a substantial proportionof, and in some embodiments consisting essentially of, HFO-1234(preferably HFO-1234ze and/or HFO-1234yf) as a replacement for existingrefrigerants, such as HFC-134a. In certain applications, therefrigerants of the present invention potentially permit the beneficialuse of larger displacement compressors, thereby resulting in betterenergy efficiency than other refrigerants, such as HFC-134a. Thereforethe refrigerant compositions of the present invention, particularlycompositions comprising HFO-1234yf and/or HFO-1234ze (preferablytransHFO-1234ze), provide the possibility of achieving a competitiveadvantage on an energy basis for refrigerant replacement applications.

It is contemplated that the compositions of the present, includingparticularly those which comprise HFO-1234yf and/or HFO-1234ze, alsohave advantage (either in original systems or when used as a replacementfor refrigerants such as CFC-11, CFC-12, HCFC-22, HFC-134a, HFC-152a,R-500 and R-507A), in chillers typically used in connection withcommercial air conditioning systems. In certain of such embodiments itis preferred to include in the present compositions, particularly thosecomprising HFO-1234yf and/or HFO-1234ze, from about 0.5 to about 30% ofa supplemental flammability suppressant, and in certain cases morepreferably 0.5% to about 15% by weight and even more preferably fromabout 0.5 to about 10% on a weight basis. In this regard it is notedthat the certain of HFO-1234 and/or HFO-1225 components of the presentcompositions may in certain embodiments act as flammability suppressantswith respect to other components in the composition. Thus, componentsother than HFO-1234 and HFO-1225 which have flammability suppressantfunctionality in the composition will sometimes be referred to herein asa supplemental flammability suppressant.

In certain preferred embodiments, the present compositions include, inaddition to the compounds of formula I, particularly HFO-1234 (includingHFO-1234ze and HFO-1234yf), one or more of the following additionalcompounds that may be included primarily for their impact on the heattransfer characteristics, cost and the like. The following componentsmay thus be included in the compositions as co-heat transfer fluids (orco-refrigerants in the case of cooling operations):

Trichlorofluoromethane (CFC-11)

Dichlorodifluoromethane (CFC-12)

Difluoromethane (HFC-32)

Pentafluoroethane (HFC-125)

1,1,2,2-tetrafluoroethane (HFC-134)

1,1,1,2-Tetrafluoroethane (HFC-134a)

Difluoroethane (HFC-152a)

1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea)

1,1,1,3,3,3-hexafluoropropane (HFC-236fa)

1,1,1,3,3-pentafluoropropane (HFC-245fa)

1,1,1,3,3-pentafluorobutane (HFC-365mfc)

water

CO₂

Blowing Agents, Foams and Foamable Compositions

Blowing agents may also comprise or constitute one or more of thepresent compositions. As mentioned above, the compositions of thepresent invention may include the compounds of the present invention inwidely ranging amounts. It is generally preferred, however, that forpreferred compositions for use as blowing agents in accordance with thepresent invention, compound(s) in accordance with Formula I, and evenmore preferably Formula II, are present in an amount that is at leastabout 5% by weight, and even more preferably at least about 15% byweight, of the composition. In certain preferred embodiments, theblowing agent comprises at least about 50% by weight of the presentcompositions, and in certain embodiments the blowing agent consistsessentially of the present compositions. In certain preferredembodiments, the blowing agent compositions of the present invention andinclude, in addition to HFO-1234 (preferably HFO-1234ze and/orHFO-1234yf) one or more of co-blowing agents, fillers, vapor pressuremodifiers, flame suppressants, stabilizers and like adjuvants. By way ofexample, one or more of the following components may included in certainpreferred blowing agent of the present invention in widely varyingamounts:

Difluoromethane (HFC-32)

Pentafluoroethane (HFC-125)

1,1,2,2-tetrafluoroethane (HFC-134)

1,1,1,2-Tetrafluoroethane (HFC-134a)

Difluoroethane (HFC-152a)

1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea)

1,1,1,3,3,3-hexafluoropropane (HFC-236fa)

1,1,1,3,3-pentafluoropropane (HFC-245fa)

1,1,1,3,3-pentafluorobutane (HFC-365mfc)

water

CO₂

It is contemplated that the blowing agent compositions of the presentinvention may comprise, preferably in amounts of at least about 15% byweight of the composition, HFO-1234yf, cisHFO-1234ze, transHFO1234ze orcombinations of two or more of these. In certain preferred embodiments,the blowing agent compositions of the present invention comprise acombination of cisHFO-1234ze and transHFO1234ze in a cis:trans weightratio of from about 1:99 to about 10:99, and even more preferably fromabout 1:99 to about 5:95.

In other embodiments, the invention provides foamable compositions. Thefoamable compositions of the present invention generally include one ormore components capable of forming foam having a generally cellularstructure and a blowing agent in accordance with the present invention.In certain embodiments, the one or more components comprise athermosetting composition capable of forming foam and/or foamablecompositions. Examples of thermosetting compositions includepolyurethane and polyisocyanurate foam compositions, and also phenolicfoam compositions. In such thermosetting foam embodiments, one or moreof the present compositions are included as or part of a blowing agentin a foamable composition, or as a part of a two or more part foamablecomposition, which preferably includes one or more of the componentscapable of reacting and/or foaming under the proper conditions to form afoam or cellular structure. In certain other embodiments, the one ormore components comprise thermoplastic materials, particularlythermoplastic polymers and/or resins. Examples of thermoplastic foamcomponents include polyolefins, such as polystyrene (PS), polyethylene(PE), polypropylene (PP) and polyethyleneterepthalate (PET), and foamsformed there from, preferably low-density foams. In certain embodiments,the thermoplastic foamable composition is an extrudable composition.

The invention also relates to foam, and preferably closed cell foam,prepared from a polymer foam formulation containing a blowing agentcomprising the compositions of the invention. In yet other embodiments,the invention provides foamable compositions comprising thermoplastic orpolyolefin foams, such as polystyrene (PS), polyethylene (PE),polypropylene (PP) and polyethyleneterpthalate (PET) foams, preferablylow-density foams.

It will be appreciated by those skilled in the art, especially in viewof the disclosure contained herein, that the order and manner in whichthe blowing agent of the present invention is formed and/or added to thefoamable composition does not generally affect the operability of thepresent invention. For example, in the case of extrudable foams, it ispossible that the various components of the blowing agent, and even thecomponents of the present composition, be not be mixed in advance ofintroduction to the extrusion equipment, or even that the components arenot added to the same location in the extrusion equipment. Thus, incertain embodiments it may be desired to introduce one or morecomponents of the blowing agent at first location in the extruder, whichis upstream of the place of addition of one or more other components ofthe blowing agent, with the expectation that the components will cometogether in the extruder and/or operate more effectively in this manner.Nevertheless, in certain embodiments, two or more components of theblowing agent are combined in advance and introduced together into thefoamable composition, either directly or as part of premix which is thenfurther added to other parts of the foamable composition.

In certain preferred embodiments, dispersing agents, cell stabilizers,surfactants and other additives may also be incorporated into theblowing agent compositions of the present invention. Surfactants areoptionally but preferably added to serve as cell stabilizers. Somerepresentative materials are sold under the names of DC-193, B-8404, andL-5340 which are, generally, polysiloxane polyoxyalkylene blockco-polymers such as those disclosed in U.S. Pat. Nos. 2,834,748,2,917,480, and 2,846,458, each of which is incorporated herein byreference. Other optional additives for the blowing agent mixture mayinclude flame retardants such as tri(2-chloroethyl)phosphate,tri(2-chloropropyl)phosphate, tri(2,3-dibromopropyl)-phosphate,tri(1,3-dichloropropyl)phosphate, diammonium phosphate, varioushalogenated aromatic compounds, antimony oxide, aluminum trihydrate,polyvinyl chloride, and the like.

Any of the methods well known in the art, such as those described in“Polyurethanes Chemistry and Technology,” Volumes I and II, Saunders andFrisch, 1962, John Wiley and Sons, New York, N.Y., which is incorporatedherein by reference, may be used or adapted for use in accordance withthe foam embodiments of the present invention.

Propellant and Aerosol Compositions

In another aspect, the present invention provides propellantcompositions comprising or consisting essentially of a composition ofthe present invention. In certain preferred embodiments, such propellantcomposition is preferably a sprayable composition, either alone or incombination with other known propellants.

In one aspect, the present compositions may be used for propellingobjects, including solid and/or liquid objects and/or gaseous objects,by applying to such objects a force generated by the presentcomposition, such as would occur through the expansion of thecompositions of the present invention. For example, such force maypreferably be provided, at least in part, by the change of phase of thecompositions of the present invention from liquid to gas, and/or by theforce released as a result of a substantial pressure reduction as thecomposition of the present invention exits from a pressurized container.In this way, the compositions of the present invention may be used toapply a burst of force, or a sustained force to an object to bepropelled. Accordingly, the present invention comprises systems,containers and devices which include compositions of the presentinvention and which are configured to propel or move an object, either aliquid object or a solid object or a gaseous object, with the desiredamount of force. Examples of such uses include containers (such aspressurized cans and similar devices) which may be used, through thepropellant force, to unblock drains, pipes or blockages in conduits,channels or nozzles. Another application includes use of the presentcomposition to propel solid objects through the environment,particularly the ambient air, such as bullets, pellets, grenades, nets,canisters, bean bags, electrodes or other individual tethered oruntethered projectiles. In other embodiments, the present compositionsmay be used to impart motion, such as a spitting motion, to gyroscopes,centrifuges, toys or other bodies to be rotated, or to impart apropelling force to solid objects, such as fireworks, confetti, pellets,munitions and other solid objects. In other applications, the forceprovided by the compositions of the present invention may be used topush or steer bodies in motion, including rockets or other projectiles.

The propellant compositions of the present invention preferably comprisea material to be sprayed and a propellant comprising, consistingessentially of, or consisting of a composition in accordance with thepresent invention. Inert ingredients, solvents, and other materials mayalso be present in the sprayable mixture. Preferably, the sprayablecomposition is an aerosol. Suitable materials to be sprayed include,without limitation, cosmetic materials such as deodorants, perfumes,hair sprays, cleaning solvents, and lubricants, as well as medicinalmaterials such as anti-asthma medications. The term medicinal materialsis used herein in its broadest sense to include any and all materialswhich are, or at least are believe to be, effective in connection withtherapeutic treatments, diagnostic methods, pain relief, and similartreatments, and as such would include for example drugs and biologicallyactive substances. The medicinal material in certain preferredembodiments are adapted to be inhaled. The medicament or othertherapeutic agent is preferably present in the composition in atherapeutic amount, with a substantial portion of the balance of thecomposition comprising a compound of Formula I of the present invention,preferably HFO-1234, and even more preferably HFO-1234ze and/orHFO-1234yf.

Aerosol products for industrial, consumer or medical use typicallycontain one or more propellants along with one or more activeingredients, inert ingredients or solvents. The propellant provides theforce that expels the product in aerosolized form. While some aerosolproducts are propelled with compressed gases like carbon dioxide,nitrogen, nitrous oxide and even air, most commercial aerosols useliquefied gas propellants. The most commonly used liquefied gaspropellants are hydrocarbons such as butane, isobutane, and propane.Dimethyl ether and HFC-152a (1,1-difluoroethane) are also used, eitheralone or in blends with the hydrocarbon propellants. Unfortunately, allof these liquefied gas propellants are highly flammable and theirincorporation into aerosol formulations will often result in flammableaerosol products.

Applicants have come to appreciate the continuing need for nonflammable,liquefied gas propellants with which to formulate aerosol products. Thepresent invention provides compositions of the present invention,particularly and preferably compositions comprising HFO-1234, and evenmore preferably HFO-1234ze, for use in certain industrial aerosolproducts, including for example spray cleaners, lubricants, and thelike, and in medicinal aerosols, including for example to delivermedications to the lungs or mucosal membranes. Examples of this includesmetered dose inhalers (MDIs) for the treatment of asthma and otherchronic obstructive pulmonary diseases and for delivery of medicamentsto accessible mucous membranes or intranasally. The present inventionthus includes methods for treating ailments, diseases and similar healthrelated problems of an organism (such as a human or animal) comprisingapplying a composition of the present invention containing a medicamentor other therapeutic component to the organism in need of treatment. Incertain preferred embodiments, the step of applying the presentcomposition comprises providing a MDI containing the composition of thepresent invention (for example, introducing the composition into theMDI) and then discharging the present composition from the MDI.

The compositions of the present invention, particularly compositionswhich comprise or consist essentially of HFO-1234ze, are capable ofproviding nonflammable, liquefied gas propellant and aerosols that donot contribute substantially to global warming. The present compositionscan be used to formulate a variety of industrial aerosols or othersprayable compositions such as contact cleaners, dusters, lubricantsprays, and the like, and consumer aerosols such as personal careproducts, household products and automotive products. HFO-1234ze isparticularly preferred for use as an important component of propellantcompositions for in medicinal aerosols such as metered dose inhalers.The medicinal aerosol and/or propellant and/or sprayable compositions ofthe present invention in many applications include, in addition tocompound of formula (I) or (II) (preferably HFO-1234ze), a medicamentsuch as a beta-agonist, a corticosteroid or other medicament, and,optionally, other ingredients, such as surfactants, solvents, otherpropellants, flavorants and other excipients. The compositions of thepresent invention, unlike many compositions previously used in theseapplications, have good environmental properties and are not consideredto be potential contributors to global warming. The present compositionstherefore provide in certain preferred embodiments substantiallynonflammable, liquefied gas propellants having very low Global Warmingpotentials.

Flavorants and Fragrances

The compositions of the present invention also provide advantage whenused as part of, and in particular as a carrier for, flavor formulationsand fragrance formulations. The suitability of the present compositionsfor this purpose is demonstrated by a test procedure in which 0.39 gramsof Jasmone were put into a heavy walled glass tube. 1.73 grams ofR-1234ze were added to the glass tube. The tube was then frozen andsealed. Upon thawing the tube, it was found that the mixture had oneliquid phase. The solution contained 20 wt. % Jasome and 80 wt. %R-1234ze, thus establishing favorable use a carrier for flavorformulations and fragrances. It also establishes its potential as anextractant of biologically active compounds (such as Biomass) andfragrances, including from plant matter. In certain embodiments, it maybe preferred to use the present composition for in extractionapplications with the present fluid in its supercritical state. This another applications of involving use of the present compositions in thesupercritical or near supercritical state are described hereinafter.

Inflating Agents

One potential advantage of the compositions of the present invention isthat the preferred compositions are in a gaseous state under mostambient conditions. This characteristic allows them to fill the spacewhile not adding significantly to the weight of the space being spilled.Furthermore, the compositions of the present invention are able to becompressed or liquefied for relatively easy transportation and storage.Thus, for example, the compositions of the present invention may beincluded, preferably but not necessarily in liquid form, in a closedcontainer, such as a pressurized can, which has a nozzle therein adaptedto release the composition into another environment in which it willexist, at least for a period of time, as a pressurized gas. For example,such an application may include including the present compositions in acan adapted to connect to tires such as may be used on transportationvehicles (including cars, trucks and aircraft). Other examples inaccordance with this embodiment include the use of the presentcompositions, in a similar arrangement, to inflate air bags or otherbladders (including other protective bladders) adapted to contain, atleast for a period of time, a gaseous material under pressure.Alternatively to the use of a fixed container, such as I can, thepresent compositions may be applied in accordance with this aspect ofthe invention through a hose or other system that contains the presentcomposition, either in liquid or gaseous form, and through which it canbe introduced into such a pressurized environment as is required for theparticular application.

Methods and Systems

The compositions of the present invention are useful in connection withnumerous methods and systems, including as heat transfer fluids inmethods and systems for transferring heat, such as refrigerants used inrefrigeration, air conditioning and heat pump systems. The presentcompositions are also advantageous for in use in systems and methods ofgenerating aerosols, preferably comprising or consisting of the aerosolpropellant in such systems and methods. Methods of forming foams andmethods of extinguishing and suppressing fire are also included incertain aspects of the present invention. The present invention alsoprovides in certain aspects methods of removing residue from articles inwhich the present compositions are used as solvent compositions in suchmethods and systems.

Heat Transfer Methods and Systems

The preferred heat transfer methods generally comprise providing acomposition of the present invention and causing heat to be transferredto or from the composition, either by sensible heat transfer, phasechange heat transfer, or a combination of these. For example, in certainpreferred embodiments the present methods provide refrigeration systemscomprising a refrigerant of the present invention and methods ofproducing heating or cooling by condensing and/or evaporating acomposition of the present invention. In certain preferred embodiments,the methods for cooling, including cooling of other fluid eitherdirectly or indirectly or a body directly or indirectly, comprisecondensing a refrigerant composition comprising a composition of thepresent invention and thereafter evaporating said refrigerantcomposition in the vicinity of the article to be cooled. As used herein,the term “body” is intended to refer not only to inanimate objects butalso to living tissue, including animal tissue in general and humantissue in particular. For example, certain aspects of the presentinvention involve application of the present composition to human tissuefor one or more therapeutic purposes, such as a pain killing technique,as a preparatory anesthetic, or as part of a therapy involving reducingthe temperature of the body being treated. In certain embodiments, theapplication to the body comprises providing the present compositions inliquid form under pressure, preferably in a pressurized container havinga one-way discharge valve and/or nozzle, and releasing the liquid fromthe pressurized container by spraying or otherwise applying thecomposition to the body. As the liquid evaporates from the surface beingsprayed, the surface cools.

Certain preferred methods for heating a fluid or body comprisecondensing a refrigerant composition comprising a composition of thepresent invention in the vicinity of the fluid or body to be heated andthereafter evaporating said refrigerant composition. In light of thedisclosure herein, those of skill in the art will be readily able toheat and cool articles according to the present inventions without undueexperimentation.

Applicants have found that in the systems and methods of the presentinvention many of the important refrigeration system performanceparameters are relatively close to the parameters for R-134a. Since manyexisting refrigeration systems have been designed for R-134a, or forother refrigerants with properties similar to R-134a, those skilled inthe art will appreciate the substantial advantage of a low GWP and/or alow ozone depleting refrigerant that can be used as replacement forR-134a or like refrigerants with relatively minimal modifications to thesystem. It is contemplated that in certain embodiments the presentinvention provides retrofitting methods which comprise replacing theheat transfer fluid (such as a refrigerant) in an existing system with acomposition of the present invention, without substantial modificationof the system. In certain preferred embodiments the replacement step isa drop-in replacement in the sense that no substantial redesign of thesystem is required and no major item of equipment needs to be replacedin order to accommodate the composition of the present invention as theheat transfer fluid. In certain preferred embodiments, the methodscomprise a drop-in replacement in which the capacity of the system is atleast about 70%, preferably at least about 85%, and even more preferablyat least about 90% of the system capacity prior to replacement. Incertain preferred embodiments, the methods comprise a drop-inreplacement in which the suction pressure and/or the discharge pressureof the system, and even more preferably both, is/are at least about 70%,more preferably at least about 90% and even more preferably at leastabout 95% of the suction pressure and/or the discharge pressure prior toreplacement. In certain preferred embodiments, the methods comprise adrop-in replacement in which the mass flow of the system is at leastabout 80%, and even more preferably at least 90% of the mass flow priorto replacement.

In certain embodiments the present invention provides cooling byabsorbing heat from a fluid or body, preferably by evaporating thepresent refrigerant composition in the vicinity of the body or fluid tobe cooled to produce vapor comprising the present composition.Preferably the methods include the further step of compressing therefrigerant vapor, usually with a compressor or similar equipment toproduce vapor of the present composition at a relatively elevatedpressure. Generally, the step of compressing the vapor results in theaddition of heat to the vapor, thus causing an increase in thetemperature of the relatively high pressure vapor. Preferably in suchembodiments the present methods include removing from this relativelyhigh temperature, high pressure vapor at least a portion of the heatadded by the evaporation and compression steps. The heat removal steppreferably includes condensing the high temperature, high pressure vaporwhile the vapor is in a relatively high pressure condition to produce arelatively high pressure liquid comprising a composition of the presentinvention. This relatively high pressure liquid preferably thenundergoes a nominally isoenthalpic reduction in pressure to produce arelatively low temperature, low pressure liquid. In such embodiments, itis this reduced temperature refrigerant liquid which is then vaporizedby heat transferred from the body or fluid to be cooled.

In another process embodiment of the invention, the compositions of theinvention may be used in a method for producing heating which comprisescondensing a refrigerant comprising the compositions in the vicinity ofa liquid or body to be heated. Such methods, as mentioned hereinbefore,frequently are reverse cycles to the refrigeration cycle describedabove.

Foam Blowing Methods

One embodiment of the present invention relates to methods of formingfoams, and preferably polyurethane and polyisocyanurate foams. Themethods generally comprise providing a blowing agent composition of thepresent inventions, adding (directly or indirectly) the blowing agentcomposition to a foamable composition, and reacting the foamablecomposition under the conditions effective to form a foam or cellularstructure, as is well known in the art. Any of the methods well known inthe art, such as those described in “Polyurethanes Chemistry andTechnology,” Volumes I and II, Saunders and Frisch, 1962, John Wiley andSons, New York, N.Y., which is incorporated herein by reference, may beused or adapted for use in accordance with the foam embodiments of thepresent invention. In general, such preferred methods comprise preparingpolyurethane or polyisocyanurate foams by combining an isocyanate, apolyol or mixture of polyols, a blowing agent or mixture of blowingagents comprising one or more of the present compositions, and othermaterials such as catalysts, surfactants, and optionally, flameretardants, colorants, or other additives.

It is convenient in many applications to provide the components forpolyurethane or polyisocyanurate foams in pre-blended formulations. Mosttypically, the foam formulation is pre-blended into two components. Theisocyanate and optionally certain surfactants and blowing agentscomprise the first component, commonly referred to as the “A” component.The polyol or polyol mixture, surfactant, catalysts, blowing agents,flame retardant, and other isocyanate reactive components comprise thesecond component, commonly referred to as the “B” component.Accordingly, polyurethane or polyisocyanurate foams are readily preparedby bringing together the A and B side components either by hand mix forsmall preparations and, preferably, machine mix techniques to formblocks, slabs, laminates, pour-in-place panels and other items, sprayapplied foams, froths, and the like. Optionally, other ingredients suchas fire retardants, colorants, auxiliary blowing agents, and even otherpolyols can be added as a third stream to the mix head or reaction site.Most preferably, however, they are all incorporated into one B-componentas described above.

It is also possible to produce thermoplastic foams using thecompositions of the invention. For example, conventional polystyrene andpolyethylene formulations may be combined with the compositions in aconventional manner to produce rigid foams.

Cleaning Methods

The present invention also provides methods of removing containmentsfrom a product, part, component, substrate, or any other article orportion thereof by applying to the article a composition of the presentinvention. For the purposes of convenience, the term “article” is usedherein to refer to all such products, parts, components, substrates, andthe like and is further intended to refer to any surface or portionthereof. Furthermore, the term “contaminant” is intended to refer to anyunwanted material or substance present on the article, even if suchsubstance is placed on the article intentionally. For example, in themanufacture of semiconductor devices it is common to deposit aphotoresist material onto a substrate to form a mask for the etchingoperation and to subsequently remove the photoresist material from thesubstrate. The term “contaminant” as used herein is intended to coverand encompass such a photo resist material.

Preferred methods of the present invention comprise applying the presentcomposition to the article. Although it is contemplated that numerousand varied cleaning techniques can employ the compositions of thepresent invention to good advantage, it is considered to be particularlyadvantageous to use the present compositions in connection withsupercritical cleaning techniques. Supercritical cleaning is disclosedin U.S. Pat. No. 6,589,355, which is assigned to the assignee of thepresent invention and incorporated herein by reference. Forsupercritical cleaning applications, is preferred in certain embodimentsto include in the present cleaning compositions, in addition to theHFO-1234 (preferably HFO-1234ze), one or more additional components,such as CO₂ and other additional components known for use in connectionwith supercritical cleaning applications. It may also be possible anddesirable in certain embodiments to use the present cleaningcompositions in connection with particular vapor degreasing and solventcleaning methods.

Flammability Reduction Methods

According to certain other preferred embodiments, the present inventionprovides methods for reducing the flammability of fluids, said methodscomprising adding a compound or composition of the present invention tosaid fluid. The flammability associated with any of a wide range ofotherwise flammable fluids may be reduced according to the presentinvention. For example, the flammability associated with fluids such asethylene oxide, flammable hydrofluorocarbons and hydrocarbons,including: HFC-152a, 1,1,1-trifluoroethane (HFC-143a), difluoromethane(HFC-32), propane, hexane, octane, and the like can be reduced accordingto the present invention. For the purposes of the present invention, aflammable fluid may be any fluid exhibiting flammability ranges in airas measured via any standard conventional test method, such as ASTME-681, and the like.

Any suitable amounts of the present compounds or compositions may beadded to reduce flammability of a fluid according to the presentinvention. As will be recognized by those of skill in the art, theamount added will depend, at least in part, on the degree to which thesubject fluid is flammable and the degree to which it is desired toreduce the flammability thereof. In certain preferred embodiments, theamount of compound or composition added to the flammable fluid iseffective to render the resulting fluid substantially non-flammable.

Flame Suppression Methods

The present invention further provides methods of suppressing a flame,said methods comprising contacting a flame with a fluid comprising acompound or composition of the present invention. Any suitable methodsfor contacting the flame with the present composition may be used. Forexample, a composition of the present invention may be sprayed, poured,and the like onto the flame, or at least a portion of the flame may beimmersed in the composition. In light of the teachings herein, those ofskill in the art will be readily able to adapt a variety of conventionalapparatus and methods of flame suppression for use in the presentinvention.

Sterilization Methods

Many articles, devices and materials, particularly for use in themedical field, must be sterilized prior to use for the health and safetyreasons, such as the health and safety of patients and hospital staff.The present invention provides methods of sterilizing comprisingcontacting the articles, devices or material to be sterilized with acompound or composition of the present invention comprising a compoundof Formula I, preferably HFO-1234, and even more preferably HFO-1234ze,in combination with one or more sterilizing agents. While manysterilizing agents are known in the art and are considered to beadaptable for use in connection with the present invention, in certainpreferred embodiments sterilizing agent comprises ethylene oxide,formaldehyde, hydrogen peroxide, chlorine dioxide, ozone andcombinations of these. In certain embodiments, ethylene oxide is thepreferred sterilizing agent. Those skilled in the art, in view of theteachings contained herein, will be able to readily determine therelative proportions of sterilizing agent and the present compound(s) tobe used in connection with the present sterilizing compositions andmethods, and all such ranges are within the broad scope hereof. As isknown to those skilled in the art, certain sterilizing agents, such asethylene oxide, are relatively flammable components, and the compound(s)in accordance with the present invention are included in the presentcompositions in amounts effective, together with other componentspresent in the composition, to reduce the flammability of thesterilizing composition to acceptable levels.

The sterilization methods of the present invention may be either high orlow-temperature sterilization of the present invention involves the useof a compound or composition of the present invention at a temperatureof from about 250° F. to about 270° F., preferably in a substantiallysealed chamber. The process can be completed usually in less than about2 hours. However, some articles, such as plastic articles and electricalcomponents, cannot withstand such high temperatures and requirelow-temperature sterilization. In low temperature sterilization methods,the article to be sterilized is exposed to a fluid comprising acomposition of the present invention at a temperature of from about roomtemperature to about 200° F., more preferably at a temperature of fromabout room temperature to about 100° F.

The low-temperature sterilization of the present invention is preferablyat least a two-step process performed in a substantially sealed,preferably air tight, chamber. In the first step (the sterilizationstep), the articles having been cleaned and wrapped in gas permeablebags are placed in the chamber. Air is then evacuated from the chamberby pulling a vacuum and perhaps by displacing the air with steam. Incertain embodiments, it is preferable to inject steam into the chamberto achieve a relative humidity that ranges preferably from about 30% toabout 70%. Such humidities may maximize the sterilizing effectiveness ofthe sterilant which is introduced into the chamber after the desiredrelative humidity is achieved. After a period of time sufficient for thesterilant to permeate the wrapping and reach the interstices of thearticle, the sterilant and steam are evacuated from the chamber.

In the preferred second step of the process (the aeration step), thearticles are aerated to remove sterilant residues. Removing suchresidues is particularly important in the case of toxic sterilants,although it is optional in those cases in which the substantiallynon-toxic compounds of the present invention are used. Typical aerationprocesses include air washes, continuous aeration, and a combination ofthe two. An air wash is a batch process and usually comprises evacuatingthe chamber for a relatively short period, for example, 12 minutes, andthen introducing air at atmospheric pressure or higher into the chamber.This cycle is repeated any number of times until the desired removal ofsterilant is achieved. Continuous aeration typically involvesintroducing air through an inlet at one side of the chamber and thendrawing it out through an outlet on the other side of the chamber byapplying a slight vacuum to the outlet. Frequently, the two approachesare combined. For example, a common approach involves performing airwashes and then an aeration cycle.

Supercritical Methods

It is contemplated that in general many of the uses and methodsdescribed herein can be carried out with the present compositions in thesupercritical or near supercritical state. For example, the presentcompositions may be utilized in solvent and solvent extractionapplications mentioned herein, particularly for use in connection withmaterials such as alkaloids (which are commonly derived from plantsources), for example caffeine, codeine and papaverine, fororganometallic materials such as metallocenes, which are generallyuseful as catalysts, and for fragrances and flavors such as Jasmone.

The present compositions, preferably in their supercritical or nearsupercritical state, can be used in connection with methods involvingthe deposit of catalysts, particularly organometallic catalysts, onsolid supports. In one preferred embodiment, these methods include thestep of generating finely divided catalyst particles, preferably byprecipitating such catalyst particles from the present compositions inthe supercritical or near supercritical state. It is expected that incertain preferred embodiments catalysts prepared in accordance with thepresent methods will exhibit excellent activity.

It is also contemplated that certain of the MDI methods and devicesdescribed herein may utilize medicaments in finely divided form, and insuch situations it is contemplated that the present invention providesmethods which include the step of incorporating such finely dividedmedicament particles, such as albuterol, into the present fluids,preferably by dissolving such particles, in the present composition,preferably in the supercritical or near supercritical state. In caseswhere the solubility of the materials is relatively low when the presentfluids are in the supercritical or near supercritical state, it may bepreferred to use entrainers such as alcohols.

It is also contemplated that the present compositions in thesupercritical or near supercritical state may be used to clean circuitboards and other electronic materials and articles.

Certain materials may have very limited solubility in the presentcompositions, particularly when in the supercritical or nearsupercritical state. For such situations, the present compositions maybe used as anti-solvents for the precipitation of such low solubilitysolutes from solution in another supercritical or near supercriticalsolvent, such as carbon dioxide. For example, supercritical carbondioxide is utilized frequently used in the extrusion process ofthermoplastic foams, and the present compositions may be used toprecipitation certain materials contained therein.

It is contemplated also that in certain embodiments it may be desirableto utilize the present compositions when in the supercritical or nearsupercritical state as a blowing agent.

EXAMPLES

The following examples are provided for the purpose of illustrating thepresent invention but without limiting the scope thereof.

Example 1

The coefficient of performance (COP) is a universally accepted measureof refrigerant performance, especially useful in representing therelative thermodynamic efficiency of a refrigerant in a specific heatingor cooling cycle involving evaporation or condensation of therefrigerant. In refrigeration engineering, this term expresses the ratioof useful refrigeration to the energy applied by the compressor incompressing the vapor. The capacity of a refrigerant represents theamount of cooling or heating it provides and provides some measure ofthe capability of a compressor to pump quantities of heat for a givenvolumetric flow rate of refrigerant. In other words, given a specificcompressor, a refrigerant with a higher capacity will deliver morecooling or heating power. One means for estimating COP of a refrigerantat specific operating conditions is from the thermodynamic properties ofthe refrigerant using standard HFC-134a having a COP value of 1.00, acapacity value of 1.00 and a discharge temperature of 175° F.

TABLE 1 DISCHARGE REFRIGERANT Relative TEMPERATURE COMPOSTION RelativeCOP CAPACITY (° F.) HFO 1225ye 1.02 0.76 158 HFO trans-1234ze 1.04 0.70165 HFO cis-1234ze 1.13 0.36 155 HFO 1234yf 0.98 1.10 168

This example shows that certain of the preferred compounds for use withthe present compositions each have a better energy efficiency thanHFC-134a (1.02, 1.04 and 1.13 compared to 1.00) and the compressor usingthe present refrigerant compositions will produce discharge temperatures(158, 165 and 155 compared to 175), which is advantageous since suchresult will likely leading to reduced maintenance problems. Moreover, itis evident from the above table that one embodiment of the presentinvention, namely one in which the refrigerant composition comprises,and preferably comprises at least about 70% by weight of HFO-1234yf, hasa dramatically superior performance in terms of relative capacity incomparison not only to R-134a, but also to embodiments in which therefrigerant consists essentially of HFO-1234ze. In certain preferredembodiments, therefore the present invention provides methods forheating or cooling an article or fluid comprising using a compositioncomprising at least about 80% by weight of HFO-1234yf, and even morepreferably at least about 90% by weight, and in which the capacity ofthe refrigeration system is at least about 100%, more preferably atleast about 105%, of the capacity of the same system with R-134a used asthe refrigerant.

Example 2

The miscibility of HFO-1225ye and HFO-1234ze with various refrigerationlubricants is tested. The lubricants tested are mineral oil (C3), alkylbenzene (Zerol 150), ester oil (Mobil EAL 22 cc and Solest 120),polyalkylene glycol (PAG) oil more preferably at least about 105%, ofthe capacity of the same system with R-134a used as the refrigerant.

Example 2

The miscibility of HFO-1225ye and HFO-1234ze with various refrigerationlubricants is tested. The lubricants tested are mineral oil (C3), alkylbenzene (Zerol 150), ester oil (Mobil EAL 22 cc and Solest 120),polyalkylene glycol (PAG) oil (Goodwrench Refrigeration Oil for 134asystems), and a poly(alpha-olefin) oil (CP-6005-100). For eachrefrigerant/oil combination, three compositions are tested, namely 5, 20and 50 weight percent of lubricant, with the balance of each being thecompound of the present invention being tested

The lubricant compositions are placed in heavy-walled glass tubes. Thetubes are evacuated, the refrigerant compound in accordance with thepresent invention is added, and the tubes are then sealed. The tubes arethen put into an air bath environmental chamber, the temperature ofwhich is varied from about −50° C. to 70° C. At roughly 10° C.intervals, visual observations of the tube contents are made for theexistence of one or more liquid phases. In a case where more than oneliquid phase is observed, the mixture is reported to be immiscible. In acase where there is only one liquid phase observed, the mixture isreported to be miscible. In those cases where two liquid phases wereobserved, but with one of the liquid phases occupying only a very smallvolume, the mixture is reported to be partially miscible.

The polyalkylene glycol and ester oil lubricants were judged to bemiscible in all tested proportions over the entire temperature range,except that for the HFO-1225ye mixtures with polyalkylene glycol, therefrigerant mixture was found to be immiscible over the temperaturerange of −50° C. to −30° C. and to be partially miscible over from −20to 50° C. At 50 weight percent concentration of the PAG in refrigerantand at 60°, the refrigerant/PAG mixture was miscible. At 70° C., it wasmiscible from 5 weight percent lubricant in refrigerant to 50 weightpercent lubricants in refrigerant.

Example 3

The compatibility of the refrigerant compounds and compositions of thepresent invention with PAG lubricating oils while in contact with metalsused in refrigeration and air conditioning systems is tested at 350° C.,representing conditions much more severe than are found in manyrefrigeration and air conditioning applications.

Aluminum, copper and steel coupons are added to heavy walled glasstubes. Two grams of oil are added to the tubes. The tubes are thenevacuated and one gram of refrigerant is added. The tubes are put intoan oven at 350° F. for one week and visual observations are made. At theend of the exposure period, the tubes are removed.

This procedure was done for the following combinations of oil and thecompound of the present invention:

a) HFC-1234ze and GM Goodwrench PAG oil

b) HFC1243 zf and GM Goodwrench oil PAG oil

c) HFC-1234ze and MOPAR-56 PAG oil

d) HFC-1243 zf and MOPAR-56 PAG oil

e) HFC-1225 ye and MOPAR-56 PAG oil.

In all cases, there is minimal change in the appearance of the contentsof the tube. This indicates that the refrigerant compounds andcompositions of the present invention are stable in contact withaluminum, steel and copper found in refrigeration and air conditioningsystems, and the types of lubricating oils that are likely to beincluded in such compositions or used with such compositions in thesetypes of systems.

Comparative Example

Aluminum, copper and steel coupons are added to a heavy walled glasstube with mineral oil and CFC-12 and heated for one week at 350° C., asin Example 3. At the end of the exposure period, the tube is removed andvisual observations are made. The liquid contents are observed to turnblack, indicating there is severe decomposition of the contents of thetube.

CFC-12 and mineral oil have heretofore been the combination of choice inmany refrigerant systems and methods. Thus, the refrigerant compoundsand compositions of the present invention possess significantly betterstability with many commonly used lubricating oils than the widely-usedprior art refrigerant-lubricating oil combination.

Example 4 Polyol Foam

This example illustrates the use of blowing agent in accordance with oneof the preferred embodiments of the present invention, namely the use ofHFO-1234ze, and the production of polyol foams in accordance with thepresent invention. The components of a polyol foam formulation areprepared in accordance with the following Table 2:

TABLE 2 Polyol Component PBW Voranol 490 50 Voranol 391 50 Water 0.5B-8462 (surfactant) 2.0 Polycat 8 0.3 Polycat 41 3.0 HFO-1234ze 35 Total140.8 Isocyanate M-20S 123.8 Index 1.10 *Voranol 490 is a sucrose-basedpolyol and Voranol 391 is a toluene diamine based polyol, and each arefrom Dow Chemical. B-8462 is a surfactant available fromDegussa-Goldschmidt. Polycat catalysts are tertiary amine based and areavailable from Air Products. Isocyanate M-20S is a product of Bayer LLC.The foam is prepared by first mixing the ingredients thereof, butwithout the addition of blowing agent. Two Fisher-Porter tubes are eachfilled with about 52.6 grams of the polyol mixture (without blowingagent) and sealed and placed in a refrigerator to cool and form a slightvacuum. Using gas burets, about 17.4 grams of HFO-1234ze are added toeach tube, and the tubes are then placed in an ultrasound bath in warmwater and allowed to sit for 30 minutes. The solution produced is hazy,and a vapor pressure measurement at room temperature indicates a vaporpressure of about 70 psig indicating that the blowing agent is not insolution. The tubes are then placed in a freezer at 27° F. for 2 hours.The vapor pressure was again measured and found to be 14-psig. Theisocyanate mixture, about 87.9 grams, is placed into a metal containerand placed in a refrigerator and allowed to cool to about 50° F. Thepolyol tubes were then opened and weighed into a metal mixing container(about 100 grams of polyol blend are used). The isocyanate from thecooled metal container is then immediately poured into the polyol andmixed with an air mixer with double propellers at 3000 RPM's for 10seconds. The blend immediately begins to froth with the agitation and isthen poured into an 8×8×4 inch box and allowed to foam. Because of thefroth, a cream time can not be measured. The foam has a 4-minute geltime and a 5-minute tack free time. The foam is then allowed to cure fortwo days at room temperature.

The foam is then cut to samples suitable for measuring physicalproperties and is found to have a density of 2.14 pcf. K-factors aremeasured and found to be as indicated in the following Table 3:

TABLE 3 Temperature K, BTU In/Ft² h ° F. 40° F. 0.1464 75° F. 0.1640110° F.  0.1808

Example 5 Polystyrene Foam

This example illustrates the use of blowing agent in accordance with twopreferred embodiments of the present invention, namely the use each ofthe HFCO-1234ze and HFO-1234yf, and the production of polystyrene foam.A testing apparatus and protocol has been established as an aid todetermining whether a specific blowing agent and polymer are capable ofproducing a foam and the quality of the foam. Ground polymer (DowPolystyrene 685D) and blowing agent consisting essentially of each ofthe HFCO-1234ze are combined in a vessel. The vessel volume is 200 cm³and it is made from two pipe flanges and a section of 2-inch diameterschedule 40 stainless steel pipe 4 inches long. The vessel is placed inan oven, with temperature set at from about 190° F. to about 285° F.,preferably for polystyrene at 265° F., and remains there untiltemperature equilibrium is reached.

The pressure in the vessel is then released, quickly producing a foamedpolymer. The blowing agent plasticizes the polymer as it dissolves intoit. The resulting density of the two foams thus produced using thismethod are given in Table 4 and graphed in FIG. 1 as the density of thefoams produced using trans-HFO-1234ze and HFO-1234yf. The data show thatfoam polystyrene is obtainable in accordance with the present invention.The die temperature for R1234ze with polystyrene is about 250° F.

TABLE 4 Dow polystyrene 685D Foam density (lb/ft³) T ° F.transHFO-1234ze HFO-1234yf 275 55.15 260 22.14 14.27 250 7.28 24.17 24016.93

Example 6

This example illustrates the performance of one embodiment of thepresent invention in which a refrigerant composition comprises HFO-1234wherein a large proportion, and preferably at least about 75% by weightand even more preferably at least about 90% by weight, of the HFO-1234is HFO-1234yf. More particularly, such a composition is used as areplacement for HFC-134a in four refrigerant systems. The first systemis one have an evaporator temperature (ET) of about 20° F. and condensertemperature (CT) of about 130° F. (Example 6A). For the purposes ofconvenience, such heat transfer systems, that is, systems having an ETof from about 0 to about 35 and a CT of from about 80° F. to about 130°F., are referred to herein as “medium temperature” systems. The secondsystem is one have an ET of about −10° F. and a CT of about 110° F.(Example 6B). For the purposes of convenience, such heat transfersystems, that is, systems having an evaporator temperature of from about−20° F. to about 20° F. and a CT of from about 80° F. to about 130° F.,are referred to herein as “refrig/freezer” systems. The third system isone have an ET of about of 35° F. and a CT of about 150° F. (Example6C). For the purposes of convenience, such heat transfer systems, thatis, systems having an evaporator temperature of from about 30° F. toabout 60° F. and a CT of from about 90° F. to about 200° F., arereferred to herein as “automotive AC” systems. The fourth system is onehave an ET of about 40° F. and a CT of about 60° F. (Example 6D). Forthe purposes of convenience, such heat transfer systems, that is,systems having an evaporator temperature of from about 35° F. to about50° F. and a CT of from about 80° F. to about 120° F., are referred toherein as “chiller” or “chiller AC” systems The operation of each ofsuch systems using R-134a and a refrigeration composition comprising atleast about 90% by weight of HFO-1234yf is reported in Tables 6A-Dbelow:

TABLE 6A Medium Temp Conditions 20° F. ET and 130° F. CT PerformanceProperty Units R-134a HFO-1234yf Capacity* Btu/hr 2541 2519 Rel toR-134a % 99.1% COP — 2.31 2.27 Rel to R-134a % 98.3% Discharge Press.psig 198.7 190.3 Rel to R-134a % 95.8% Suction Press. psig 18.4 22.5 Relto R-134a % 122.3% Mass Flow lb/hr 0.673 0.958 Rel to R-134a % 142.3%*Capacity per CFM of compressor displacement (Volumetric Capacity)

TABLE 6B Refrig/Freezer Temp Conditions 10° F. ET and 110° F. CTPerformance Property Units R-134a HFO-1234yf Capacity* Btu/hr 1234 1293Rel to R-134a % 104.8% COP — 1.77 1.71 Rel to R-134a % 96.6% DischargePress. psig 146.4 145.4 Rel to R-134a % 99.3% Suction Press. psig 1.96.0 Rel to R-134a % 315.8% Mass Flow lb/hr 0.342 0.427 Rel to R-134a %124.9% *Capacity per CFM of compressor displacement (VolumetricCapacity)

TABLE 6C Auto AC Temp Conditions 35° F. ET and 150° F. CT PerformanceProperty Units R-134a HFO-1234yf Capacity* Btu/hr 2754 2612 Rel toR-134a % 94.8% COP — 1.91 1.84 Rel to R-134a % 96.3% Discharge Press.psig 262.9 247.3 Rel to R-134a % 94.1% Suction Press. psig 30.4 34.5 Relto R-134a % 113.5% Mass Flow lb/hr 0.891 1.235 Rel to R-134a % 138.6%*Capacity per CFM of compressor displacement (Volumetric Capacity)

TABLE 6D Chiller Temp Conditions 40° F. ET and 95° F. CT PerformanceProperty Units R-134a HFO-1234yf Capacity* Btu/hr 4236 4060 Rel toR-134a % 95.8% COP — 6.34 6.23 Rel to R-134a % 98.3% Discharge Press.psig 113.9 113.5 Rel to R-134a % 99.6% Suction Press. psig 35.0 38.7 Relto R-134a % 110.6% Mass Flow lb/hr 1.034 1.268 Rel to R-134a % 122.6%*Capacity per CFM of compressor displacement (Volumetric Capacity)

As can be seen from the Tables above, many of the importantrefrigeration system performance parameters are relatively close to theparameters for R-134a. Since many existing refrigeration systems havebeen designed for R-134a, or for other refrigerants with propertiessimilar to R-134a, those skilled in the art will appreciate thesubstantial advantage of a low GWP and/or a low ozone depletingrefrigerant that can be used as replacement for R-134a or likerefrigerants with relatively minimal modifications to the system. It iscontemplated that in certain embodiments the present invention providedretrofitting methods which comprise replacing the refrigerant in anexisting system with a composition of the present invention, preferablya composition comprising at least about 90% by weight and/or consistsessentially of HFO-1234 and even more preferably HFO-1234yf, withoutsubstantial modification of the system. In certain preferred embodimentsthe replacement step is a drop-in replacement in the sense that nosubstantial redesign of the system is required and no major item ofequipment needs to be replaced in order to accommodate the refrigerantof the present invention.

What is claimed is:
 1. A method of replacing an existing heat transferfluid contained in an existing heat transfer system comprising replacingat least a portion of said existing heat transfer fluid with a heattransfer composition comprising HFO-1234yf, wherein said existing heattransfer fluid comprises HFC-134a.
 2. The method of claim 1 wherein saidheat transfer composition comprising at least one fluoroalkene ofFormula I has a heat transfer capacity not substantially greater thanthe heat transfer capacity of said existing refrigerant.
 3. The methodof claim 1 wherein said heat transfer composition comprising at leastone fluoroalkene of Formula I has a GWP not substantially greater thanthe GWP of said existing refrigerant.
 4. The method of claim 1 whereinsaid existing heat transfer system comprises a refrigeration system. 5.The method of claim 1 wherein said existing heat transfer systemcomprises a vapor compression refrigeration system.
 6. The method ofclaim 1 wherein said replacing step is not associated with anysubstantial modification of said existing heat transfer system.
 7. Themethod of claim 1 wherein said existing heat transfer system comprises afreezer system.
 8. The method of claim 1 wherein said existing heattransfer system is an automotive AC system.
 9. The method of claim 1wherein said existing heat transfer system is a commercial airconditioning system.
 10. The method of claim 1 wherein said existingheat transfer system is a commercial refrigeration system.
 11. Themethod of claim 10 wherein said heat transfer composition of saidreplacing step comprises from about 5% by weight to about 95% by weightof said HFO-1234yf.
 12. The method of claim 11 wherein said heattransfer composition of said replacing step has a GWP of not greaterthan about
 1000. 13. The method of claim 12 wherein said heat transfercomposition of said replacing step is non-flammable.
 14. The method ofclaim 11 wherein said heat transfer composition of said replacing stepis non-flammable.
 15. The method of claim 10 wherein said heat transfercomposition of said replacing step has a GWP of not greater than about1000.
 16. The method of claim 15 wherein said heat transfer compositionof said replacing step is non-flammable.
 17. The method of claim 10wherein said heat transfer composition of said replacing step isnon-flammable.
 18. The method of claim 1 wherein said heat transfercomposition of said replacing step comprises from about 5% by weight toabout 95% by weight of said HFO-1234yf.
 19. The method of claim 18wherein said heat transfer composition of said replacing step has a GWPof not greater than about
 1000. 20. The method of claim 19 wherein saidheat transfer composition of said replacing step is non-flammable. 21.The method of claim 18 wherein said heat transfer composition of saidreplacing step is non-flammable.
 22. The method of claim 1 wherein saidheat transfer composition of said replacing step has a GWP of notgreater than about
 1000. 23. The method of claim 22 wherein said heattransfer composition of said replacing step is non-flammable.
 24. Themethod of claim 1 wherein said heat transfer composition of saidreplacing step is non-flammable.